New thermoplastic compositions and method of making same



Patented Aug. 14, 1945 UNITED STATES PATENT OFFICE NEW THERMOPLASTICCOMPOSITIONS AND METHOD OF MAKING SAME George D. Martin, Nitro, W. Va.,assignor .to I

Monsanto Chemical Company, St. Louis, Mo., a v corporation of Delawarea-naphthyl 20 Claims.

This invention relates to new plastic products derived from rubbers andto the preparation of the same. In accordance with this invention arubber is treated with an organic phosphine halide. Any organicphosphine halide can be used in the preparation of the new products ofthis invention as for example aromatic, aliphatic and mixed aromaticaliphatic phosphine halides or mixtures thereof. While phosphine halidesin which a carbon atom of an organic radical is linked directly to thephosphorus are preferred other types may be employed. For examplephosphorus may be linked to carbon through oxygen, sulfur, nitrogen andthe like. Likewise, while chlorides are preferred for reasons ofeconomy, it has been found that useful products are produced from thefluorides, iodides andbromides.

As typical examples of organic phosphine halides which may be employedin the preparation of the new plastic materials may be men--' tioned thefollowing but the invention is by no means limited thereto: phenyldichlor phosphine, thiophendichlor phosphine, tolyl dichlor phosphine,1,3,4.- trimethyl phenyl dichlor phosphine, 1,3,5 trimethyl phenyldichlor phosphine, xylyl dichlor phosphine, biphenyl dichlor phosphine,dichlor phosphine, tetrahydro naphthyl dichlor phosphine, dichlorphosphine ,of meta diphenyl benzene, decyl phenyl dichlor phosphine,diethyl amino phenyl dichlor phosphine, dimethyl amino phenyl dichlorphosphine, tertiary butyl phenyl dichlor phosphine, ditolyl chlorphosphine, dixylyl chlor phosphine, tolyl dibrom phosphine, a-naphthyldibrom phosphine, tolyloxy dichlor phosphine, u-naphthoxy dichlorphosphine, benzyl dichlor phosphine, phosphazobenzol chloride, diphenylamino dichlor phosphine, thiophenyl dichlor phosphine, anisyl dichlorphosphine, phenetyl dichlor phosphine, meta and para hydroxy phenyldichlor phosphine, chlor phenyl dichlor phosphine, bromphenyl dichlorphosphine, ethyl phenyl. dichlor phosphine, dibenzyl dichlor phosphine,diphenyl methane dichlor phosphine, xylyl dibrom phosphine, xylyldiiluor phosphine, dinaphthyl mono chlor phosphine, naphthyl difluorphosphine, di tertiary butyl phenyl mono chlor phosphine, decyl dichlorphosphine, heptyl dichlor phosphine, heptyl difluor phosphine, decyldifluor phosphine, tolyl 'di iodo phosphine, .tolyl difluor phosphine,amyl dichlor phosphine, hexyl dichlor phosphine, butyl dichlorphosphine, amyl dibrom phosphine, diamyl mono chlor phosphine,

cymyl dichlor phosphine, dicymyl mono chlor phosphine, cymyl dibromphosphine, cymyl difiuor phosphine, retyl dichlor phosphine, retyldibrom phosphine, retyl difiuor phosphine, tetrahydro naphthyl dibromphosphine andequivalents and analogues thereof.

Since organic phosphine halides are awell known class of compoundsreference may be had to the literature for methods of preparing them.However, while the present application is not concerned with thepreparation of these intermediates and is not limited thereto, aFriedel-Crafts synthesis ofiers'certain advantages. Thus, the reactionof a phosphorus trie halide with a suitable hydrocarbon in the presenceof a Friedel-Crafts catalyst results in a composition comprising theorganic phosphine halide and catalyst and this crude composition may bereacted with a rubber without isolating the organic phosphine halide.However a certain amount of unreacted ingredients areordinarilyseparated before reacting with the rubber. After heating liquidhydrocarbons as for example xylene, toluene or petroleum ether, with aphos phorus tri halide in the presence of anhydrous aluminum chloridethere separatesfafter completion of the reaction a top layer whichconsists essentially of unreacted hydrocarbon and phosphorus tri-halideand a small amount of the desired reaction product. The top layer issimply drawn on and reserved for future preparations. The bottom layercontains the desired reaction product together with a small proportionof unreacted materials, and most of the catalyst, probably in the formof a complex organic addition product. it has been found that this crudemixture remaining after separation of the upper layer is admirablysuited for reacting directly with a rubber. While the above pictureapplies Where use is made of the proportions of catalyst given in theliterature (see LiebigsAnnalen vol. 212, p. 206, 207), it has beenfoundthat by increasing the proportion of catalyst the reaction isdriven further toward completion so that eventually no layers separate.The entire reaction mixture may then be reacted with a rubber since theproducts produced, atleast for the purposes of this invention, areequivalent to 'those described above and in fact appear to be identicalin every respect. Alternatively the crude reaction product whether abottom layer oranentire reaction mixture obtained with a higherproportion of catalyst, may be heated up 'to distill out unreactedphosphorus tri halideand hydrocarbon. Obviously the resultingproductslare not num chloride, whether crude or stripped,

containing most of the catalyst used in'the preparation will beidentified in the disclosure following and in the attached claims-as"technical hydrocarbon phosphine halides.

The following example illustrates in detail the product. It is, however,essential that the ingredients be brought into intimate and uniformassociation if it is expected to get reproducible preparation oftechnical hydrocarbon phosphine halides but is not limitative of theinvention:

Into a suitable glass or glass lined reaction r sse fitted with a lu onde se the e was chewed .ne ts by ei ht of n pa by weight of RC1: and129 parts by weight, of enbys ro le ch or de Th m xt was heated; orefluxing mpe atur a which emperature it was maintained for about ,36hours.

When cool thereaction mixture separated into H W por ions-jib bottomlayer a ou tin o u s antia ly 849P r b we d aw o f and eith r immedi tey re with a b r ore 'ore moi tur P o f. co taine s sinc tolyl dichlorphosphine analogous materials h roly e to th co e pon n o d o e hepresence o sma amoun o Water d in t e sub e u ilt e otion ith the ber hano n ticee ole'e eet.

When t e a umi um hlor d was reesedto .4. be t ,i the ab ve. pro du e nola e s separated,

. C u retyl h or Phosp ioewes p epa d by c arg ng e00 ve bs, by wei htof eohnioe reteneeoo are by eigh f P01; and s rene b weieh o .anhyorole. MC into e oitab eles o cl s d vessel eoo'he ti s. refluxin tem e a ue 1, 0} eleven hours, Sin ther was nosepa eti n o lay s the ent ereaction mixture we emmoyee e the act nt.

' e here normally so ids wil 'oo sens-fete s an nn t eo eo l q dv ayer.so tb'afl hephosbhin ha e prepared th r irom are "usually it et o in t erud reeotion mixtur byte Iso table solvent c s pe ro um eth ceoid'thereiduel fie rem al of the so vent mp oyed esthe e o o her run: ficationserves no useful purpose. However, the addition of a small proportion'ofaFriedel-Crafts atalyst, p e a l anhy rou l m m, hloride, is desirablein orderto promote the reaction with "a rubber."

Crude tolyl dibrom phosphine andtol yl di iodo phosphine can be obtained'by substituting PBrs and'PI':'respectively 'for the P013 in theprocedure 'des'cribed'for crude tolyl dichlor phosphine. Since PFs'fi sa; gas somewhat different technique must be employed to prepare theorganic phosphinefluoridesq -Although it is not possible to state withcertainty 'thenature of the change taking place upon treating rubberwitha phosphinehalide, the fact that the hydrocarbon content of the originalrubber is'materially increased indicates that reaction products of therubber are produced. The properties of the final product depend-upon thereaction conditions, the proportion of reacting-ingredients and thelike. Thus, the conditions may be varied so as to obtain addition thebatch size should-be kept well results. To this end use of a solventlike benzene, toluene or carbon disulfide is of considerable benefit. Inthe absence of a solvent the phosphine halides tend to make he rubberslimy and slippery during the early s ages of the reaction. However, aneflicient internal type mixer of corrosion resistant material such asstainless steel will give the proper association of the reactants. Thismay be of the W. 8: P. type or modifications thereof but in any case"there s ould belit le o no ree space above the mixer blades. Use ofwell bfrolgen down rubber further i litates the r c ion- A century er,or .even'en d y rubb r l ma be u the latter case it is necessary toenclose the ro l fid as a dry as th gh t ncl ure .or to work in a roomof controlled low humidity in .order to avoid hydrolysis of thephosphine ha he mtterml st b added slowly u ti the s'lipperystage has ijassed after which the rem ind rmay b added t 'a fai ly rap d rat lOWthat which would normally'bc employed in milling rubber alone. Tightrolls' and a small bank both aid the mixing. Once the reactants havebeen thoroughly mixed so that the mass is homogeneous throughout it maybe removed and placed in an ordinary oven to complete the reaction.l'hereaction between phosphine halides and'rubber takes place .over aconsiderable range of ternperatures. Thus, sjlery satisfactory re'-actions have been carried out over a period of about 48 hours wherejthetemperature was carefully,,controlled at about 47 or below durin theentire period in which the phosphine halide was in Conta t wi t rubber..At h he temperatures, as for example up toe-bout 0., the time necessary,for reaction becomes increasingly sho ter but at temper tur s much in eess of C it is rather d l u t to contro the reactions so as to obtainreproducible results.

The following specific examples will illustrate the invention in detailand are to he understood as descr pt e and plana but not limitat ve ofthe'invention.

Example .1

A rubber cement was prepared by dissolving 100 parts by weight of palecrepe rubber in a suitable-solvent as for example carbon disulficle.Into the cement so prepared contained in a suitable vessel fitted with areflux condenser and stirring mechanism there was stirred 200 parts byweight of crude naphthyl phosphine dichloride. Heat was then applied.and the mixture stirred at refluxing temperature for about 15 hoursafter which a Liebig type' condenser was substituted for the reflux,condenser and the Solve t r m v d/by d ti lat n Heatin wa continued fora short time after distillation had substantially ceased and then livesteam was introduced and after a. thorough steaming out,

of pale crepe rubber.

solvents as for example gasoline and lubricating oil. For example. astock wasmade up-as follows, the parts being by weight::. 100 parts ofthe above plastic product, 40 parts Gastex; 10 parts zinc oxide, 5 partswhiting,-3 parts stearic acid", 2 parts pine tar, 2 partsxsulfur. and1.5:parts 'mercaptobenzothiazole. .This stock gave a good cure ,in,30minutes at the temperature of forty pounds steam pressure per squareinch. The cured product showed almost no swelling in lubricating oilafter four days immersion at room temperature.

Example II Substantially 100 parts by weight of palecrepe rubber weredissolved in carbonbisulfide and reacted with 100 parts by weight ofcrude cymyl phosphine dichloride in substantially the manner describedabove except that; the refluxing period was about, 24 hours. 126 partsby weight of a tough tan rubbery material was obtained after drying toconstant weight.

Example III Substantially 100. parts by weight of pale crepe rubber weredissolved in carbon bisulfide and a mixture of substantially 9 parts byweight of anhydrous aluminum chloride and 75 parts by weight of tolyldichlor phosphine (B. P. 115-117? at 8 mm. pressure) added to. thecement so prepared. The charge was heated and stirred at refluxingtemperature for approximately 24 hours, the solvent removed and theproduct worked up all substantially as described in Example I to obtaina toughrubbery product. This product could be cured by heating in .apress in the usual manner in the presence of zinc oxide, sulfur andaccelerator. After compounding and curing in a typical-rubber formulacarrying parts by weight of carbon black the composition was found to beinsoluble in most organic solvents. After'72 hours immersion at roomtemperature a strip of the cured. stock had gained only 8.4% by weightin gasoline and 4.3% by weight in' lubricating oil.

Example IV Example V Substantially 150 parts by weight of crude tolyldibrom phosphine was added to a. carbon bisu lfide cement containing 100parts by weight The charge was stirred and heated at refluxingtemperature for. 48

hours and the solvent removed and the product worked up allsubstantially as described in Example I. The dry product (145 parts byweight) was brown in color, rubbery and non tacky. g

Eaiample VI Substantially 100 parts by weight of pale crepe rubber wasdissolved in a suitable solvent as for example carbon disulfide and 100parts by weight of crude retyl dichlor phosphine added to the cement soprepared; The charge was allowed to stand at room temperature forapproximatelyafl hours after which the solvent was removed and theresidue washed and dried all substantially as described in Example I.About 148parts ,by weight of tough rubbery product remained after dryingto constant weight. It was found that this product could be cured in apress in the usual manner after com unding with zinc oxide, sulfur andaccelerator and was reinforced by the addition of carbon black. Thecured rubber products were resistant to attack by gasoline, lubricatingoil and other solvents and were more resistant to ozone than similarstocks com pounded from pale crepe rubber.

The reaction can be effected in a shorter time by the application ofheat but conducting the reaction forlonger times at lower temperaturesgives products which. for most purposespossess somewhat betterproperties. For example the above charge was heated to refluxingtemperature for an hour and then worked up as .usual. While the weightof the final product-was the same as before the vulcanizates obtainedtherefrom 'were less resistant to ozone. Where harder products aredesired the proportion of retyl dichlor phosphine should be increased.Thus a very hard product was obtained by doubling the 40 proportion ofretyl dichlor phosphine and heating at refluxing temperature for 15hours.

Valuable products havealso been produced by substituting pale creperubber by cheaper reclaimed and scrap rubbers. For example parts byweight of ground truck peels were suspended in carbon bisulfide. and 150parts: by

weight of crude retyl dichlor phosphine added thereto. The charge washeated to refluxing temperature at which temperature it was stirred andheated for eight hours. The solventwas then removed and the productisolated, alllsubstantially as described in Example I. The weight of drytough rubbery product was l'll' parts. While some of the tensilestrength and ultimate elongation are sacrificed by replacing pale crepeby the cheaper scrap rubber, they are adequate for most purposes andvthe solvent and. ozone resistance are excellent. A stock consisting ,of100 parts by weight of the above product ob tained from truck peels, 10parts zinc oxide,,5 parts sulfur,-3 parts stearic acid, 2 parts pinetar, 1.5 parts mercaptobenzothiazole and 20 parts Gastex (all parts areby weight), after curing in a press in the usual'manner possessedatensile strength of 1030 lbs./in. and an ultimate elongation of After72 hours immersion .in gasoline, at room temperature the stock gained13.4% in weight and in lubricating oil lost 0.4% in weight. Cracking wasnegligible after three minutes exposure to ozone under stress.

Decreasing the amount of retyl dichlor. phosphine in the reaction withtruck peels rendered the product softer andmore tacky and resistance toozone was decreased. Increasingthe amount gave harder and less rubberyproducts.

* xample-VH- in Example .I tofpbtain rea r-rainy weight or I wereSubstantially 40 par-ts 'weight of pale crepe rubber was dissolved incarbon disulnde brother solventand substantially :80 parts by weight ofditolyl phosphinemono chloride added "thereto. a charge was hem-ted torefluxing temperature-aior about l5-ho"urs-, the solvent *then removedand the residue washed and'dried al-leubstantially as described in--Example I to obtain 504 parts by weight 'of softmbbery'pmduct. I

- As will be appreciated-irom the foregoing description and example,aIwide:-variety of rubbers both natural and synthetic are applicabie inthe process of the present invention; Accordingly the-term a rubber -is-employed:in theclaims to define a .vulcanizableplastic" mate-riaiiwhich possesses high extensibility under load: coupled with the propertyof iorciblyretracti-ngto *appronimately its original size and shapeaiter-the load is removed. Typical rubber-a which canbe used in thisinvention include torexample crude indla rubber, reclaimed.ru-bberpbalata, gutta percha, chlor butadienepolymers; butadienepolymers and co-polymers which include :such well known materia'ls asPerbunan-,-'I-Iycar, I Bun'a S and: Buna N; guayule, chicle, gutta-siak,juletongor pontianac,-- Gaucho, Kickxiaand Manihot rubbers, olefinepol-ysulflde plastics,-'2,3 dimethyl butadiene polymers,- z-pheny-lbutadienepolymers, dichlorbutadienepolymers, monoand di-olefineco-polymers .and the'like whether or not admixed with fillers, pigments,accelerating or vulcanizing' agents or-other compounding ingredients.

Again this inventi0n- -is n0tlimited to the specific examplesand-com=positions set iorth-to illustrate the invention. -Other solventsand other organic phosphine halides whether; the pure compounds,mixtures thereof or the crude" or stripped varieties and whether in 'thepresence or absence of a Friedel-Craftscatalyst may be used in -thepreparation of-the preferred materials aswell as other mean's ofei'fecting the reactions. In addition other Friedel-Crafts catalystssuch as ferric-chloride and stann-ic chloride may be employed- Otherfillersj'compounding and vulcanizing ingredients-than those particularlymentioned may be utilized. Furthermore the new products of thisinvention'can be admixed with other plastic or resinous mate rials. Thisinvention is limitod solely by the claims attached'hereto as part of'the present specification. 1 I

. This application is a continuation-impart of col-pending applicationsserial No. 346,991, filed July 23, 1940, and -Seria-l:No. "364',598,'filed November 6, 19.40; L

:What is claimed isc- 21. Anew composition ofmatter obtained b'yintimately mixing-a rubber :with an organic phosphine 'halide :havingatloastone halogen atom ans-2,497

and at least oneorganic 'ndicle directly attached to a trivalentphosphorus atom in :a propontim within the range equivalent to 65-200partsby weight of. crude phosphinehalide per parts of rubber and heatingthe :mixture within the range of room temperature'to C. M

*2. Anew composition of matter obtaiznd by intimately mixing a rubberwith an organic'phmphine halide having .at leastaone :halogen atom and:at least-one hydrocarbon radicle directly-ate tached to a trivalent"phosphorus-atom in .a proportion within the range equivalent to 06400parts by .weightnf -crnde sphosphine halide per 100 parts ofrubber andheating the mixturemt atemperature within the range 01 room tunperaturetocthe refluxing temperature of a cementof'therubber, x

3; A new composition of matter obtained by intimately mixingzzia rubberwith an alkyl phosphine halide having at least one halogen atom and acarbon atom of at least one alkyl group directly attached to a trivalentphosphorus atom in a proportion within the range equivalent 10 65-200parts by weight of crude phosphlne halide per 100 parts of rubber andheating the mixture at a temperature within the range of roomtemperature to -tlie =:refluxing temperature of -a cement of the rubber;

- 4. A new composition of matter obtaincd by intimately mixing a rubberwith a technical-alkyd phosphlne chloride having at least one chlorineatom and at least one alkyl radlcle directly attached to a trivalentphosphorus atom and consisting of the crude .reactionproduct containingthe catalyst complex of an aliphatic hydrocarbon containing at leastfour but less than eleven carbon atoms with PCI: in the presence ofaluminum chloride catalyst "and heating the mixture at least as high asroom temperature but no higher than refluxing temperature of a cement orthe rubber, the said phosphine haiide being in a proportion within therange of 65-200 parts-by weight per 100' parts by weight of rubber.

5. A new composition of matter obtained bylntimately mixing a rubberwith acondensed polynuclear aromatic phosphine halide comprising thestructure where R is a condensed polynuclear aromatic radicle and xandfy' are halogen in a proportion within the range equivalentto 65 200parts by weight of crude phosphinehalide' per 100 parts of rubber andheating the mixture'within' the range of room temperature to 140 C.

6. A new composition oflmatter obtained by intimately mixing indiarubber l with a condensed polynuclear aromatic phosphlne chloridecomprising the structure RY-P V where R is, a condensedpolynucleararomatic radicle in a proportion within the range equivalent to 65-200parts by weight of crude phosphine halide per 100 parts of rubber andheating the mixture within the range of room temperature to'140'C.' 7. Anew composition of matter obtained by intimately mixing india rubberwith at least an equal proportion by weight but not more than twice theweight of the rubber of a technical condensed polynuclear aryl phosphinedichloride having two chlorine atoms and one polynuclear aryl radicledirectly attached to a trivalent phosphorus atom and consisting of thecrude reaction product containing the catalyst complex of a condensedpolynuclear aryl hydrocarbon and P013 in the presence of aluminumchloride catalyst and heating the mixture at a temperature within therange of room temperature to the temperature of reflux of a cement ofthe rubber to effect a reaction characterized by the fact that thehydrocarbon content of the original rubber is materially increased.

8. A new composition of matter obtained by intimately mixing indiarubber with at least an equal proportion by weight of technical naphthyldichlor phosphine said phosphine being no more than twice the Weight ofthe rubber and having two chlorine atoms and one naphthyl radicleattached directly to a trivalent phosphorus atom and consisting of thecrude reaction product containing the catalyst complex of naphthaleneand PCIs in the presence of aluminum chloride catalyst and heating themixture within the range of room temperature to refluxing temperature ofa cement of the rubber.

9. A new composition of matter obtained by intimately mixing a reclaimedrubber with retyl dichlor phosphine comprising the structure where R isa retyl radicle in a proportion within the range equivalent to 65-200parts by weight of crude retyl phosphine dichloride and heating themixture within the range of room tempera ture to the refluxingtemperature of a cement of the rubber.

10. A new composition of matter obtained by intimately mixing areclaimed rubber with substantially 150 arts by weight per 100 parts byweight of rubber of technical retyl dichlor phosphine having twochlorine atoms and one retyl radicle directly attached to a trivalentphosphorus atom consisting of the crude reaction product containing thecatalyst complex of technical retene and P013 in the presence ofaluminum chloride and heating the mixture within the range of roomtemperature to the refluxing temperature of a cement of the rubber.

11. The method of making a new composition of matter which comprisesintimately mixing a rubber with an organic phosphine halide having atleast one halogen atom and at least one organic radicle directlyattached to a trivalent phosphorus atom in a proportion within the rangeequivalent to 623-200 parts by weight of crude phosphine halide per 100parts of rubber and heating the mixture within the range of roomtemperature to 140 C.

12.'The method of making a new composition of matter which comprisesintimately mixing a rubber with an organic phosphine halide having atleast one halogen atom and at least one hydrocarbon radicle directlyattached to a trivalent phosphorus atom in a proportion within the rangeequivalent to 655-200 parts by weight of crude phosphine halide per 100parts of rubber and heating the mixture at a temperature within therange of room temperature to the refluxing temperature of a cement ofthe rubber.

13. The method of making a new composition of matter which comprisesintimately mixing a rubber with an alkyl phosphine halide having atleast one halogen atom and a carbon atom of at least one alkyl groupdirectly attached to a trivalent phosphorus atom in a proportion withberand heating the mixture at a temperature within the range ofroomtempe'rature to the refluxing temperature of a cement of the rubber.

14. The method of making a new composition of matter which comprisesintimately mixing a rubber with a technical alkyl phosphine chloridehaving at least one chlorine atom'and at lea'st one alkyl radicledirectly attached to a trivalent" phosphorus atom and consisting of thecrude reaction product containing 'the catalyst complex of an aliphatichydrocarbon containing at least four but less than eleven carbon atomswith P013 in the presence of aluminum chloride catalyst and heating themixture at least as high as room temperature but no higher thanrefluxing temperature of a cement of the rubber, the said phosphinehalide being in a proportion within the range of 65-200 parts by weightper parts by weight of rubber.

15. The method of making a new composition of matter which comprisesintimately mixing a rubber with a condensed polynuclear aromaticphosphine halide comprising the structure where R is a condensedpolynuclear aromatic radicle and :c and y are halogen in a proportionwithin the range equivalent to 651-200 parts by weight of crudephosphine halide per 100 parts of rubber and heating the mixture withinthe range of room temperature to C.

16. The method of making a new composition of matter which comprisesintimately mixing india rubber with a condensed polynuclear aromaticphosphine chloride comprising the structure where R. is a condensedpolynuclear aromatic radicle in a proportion within the range equivalentto 65-200 parts by weight of crude phosphine halide per 100 parts ofrubber and heating the mixture within the range of room temperature to140 C.

17. The method of making a new composition of matter which comprisesintimately mixing india rubber with at least an equal proportion byweight but not more than twice the weight of the rubber of a technicalcondensed polynuclear aryl phosphine dichloride having two chlorineatoms and one polynuclear aryl radicle directly attached to a trivalentphosphorus atom and consisting of the crude reaction product containingthe catalyst complex of a condensed polynuclear aryl hydrocarbon andPC13 in the presence of aluminum chloride catalyst and heating themixture at a temperature within the range of room temperature to thetemperature of reflux of a cement of the rubber to effect a reactioncharacterized by the fact that the hydrocarbon content of the originalrubber is materially increased.

18. The method of making a new composition of matter which comprisesintimately mixing heating the mixture within the range of room 1otemperature to refluxing temperature of a cement of the rubber;

L9. The methods of making a new composition of matter which comprisesintimately mixing a reclaimed rubber. with retyh dichlor phosphine 1acomprising the structure l RP\ where R is a. retyl rad-icle in aproportion within the range equivalent to 65-200 parts byweight.

of crude retyl phosphine dichloride andheating the mixture within therange of roomtemperature. to the refluxing temperature of acement of therubber.

20. The method of making a new compositioni of. matter which comprisesintimately mixing a.

reclaimed" rubber with substantially 150' parts by weight per 100 parts.by weight of rubberkof technicalretyl di'chlor' phosph-ine having twochlorine atoms and one retyl radicle directly attached to' a trivalentphosphorus atom consisting of the crude reaction product containing.

the catalyst complex of technical retene and PC]: in the presence ofaluminum chloride: and V heating. the mixture within the range. of roomtemperature to the refluxing temperature 05 a cement or the rubber. i

GEORGE D. MART-LN.

